2,991 research outputs found
Orientations of the lamellar phase of block copolymer melts under oscillatory shear flow
We develop a theory to describe the reorientation phenomena in the lamellar
phase of block copolymer melt under reciprocating shear flow. We show that
similar to the steady-shear, the oscillating flow anisotropically suppresses
fluctuations and gives rise to the parallel-perpendicular orientation
transition. The experimentally observed high-frequency reverse transition is
explained in terms of interaction between the melt and the shear-cell walls.Comment: RevTex, 3 pages, 1 figure, submitted to PR
The Crystal Structure of the Extracellular 11-heme Cytochrome UndA Reveals a Conserved 10-heme Motif and Defined Binding Site for Soluble Iron Chelates
Members of the genus Shewanella translocate deca- or undeca-heme cytochromes to the external cell surface thus enabling respiration using extracellular minerals and polynuclear Fe(III) chelates. The high resolution structure of the first undeca-heme outer membrane cytochrome, UndA, reveals a crossed heme chain with four potential electron ingress/egress sites arranged within four domains. Sequence and structural alignment of UndA and the deca-heme MtrF reveals the extra heme of UndA is inserted between MtrF hemes 6 and 7. The remaining UndA hemes can be superposed over the heme chain of the decaheme MtrF, suggesting that a ten heme core is conserved between outer membrane cytochromes. The UndA structure has also been crystallographically resolved in complex with substrates, an Fe(III)-nitrilotriacetate dimer or an Fe(III)-citrate trimer. The structural resolution of these UndA-Fe(III)-chelate complexes provides a rationale for previous kinetic measurements on UndA and other outer membrane cytochromes
Orientational phase transitions in the hexagonal phase of a diblock copolymer melt under shear flow
We generalize the earlier theory by Fredrickson [J. Rheol. v.38, 1045 (1994)]
to study the orientational behaviour of the hexagonal phase of diblock
copolymer melt subjected to steady shear flow. We use symmetry arguments to
show that the orientational ordering in the hexagonal phase is a much weaker
effect than in the lamellae. We predict the parallel orientation to be stable
at low and the perpendicular orientation at high shear rates. Our analysis
reproduces the experimental results by Tepe et al. [Macromolecules v.28, 3008
(1995)] and explains the difficulties in experimental observation of the
different orientations in the hexagonal phase.Comment: 21 pages, 6 eps figures, submitted to Physical Review
Shear Alignment and Instability of Smectic Phases
We consider the shear flow of well-aligned one-component smectic phases, such
as thermotropic smectics and lamellar diblock copolymers, below the critical
region. We show that, as a result of thermal fluctuations of the layers,
parallel () alignment is generically unstable and perpendicular ()
alignment is stable against long-wavelength undulations. We also find,
surprisingly, that both and are stable for a narrow window of values
for the anisotropic viscosity.Comment: To appear in PRL. Revtex, 1 figure
Influence of confinement on the orientational phase transitions in the lamellar phase of a block copolymer melt under shear flow
In this work we incorporate some real-system effects into the theory of
orientational phase transitions under shear flow (M. E. Cates and S. T. Milner,
Phys. Rev. Lett. v.62, p.1856 (1989) and G. H. Fredrickson, J. Rheol. v.38,
p.1045 (1994)). In particular, we study the influence of the shear-cell
boundaries on the orientation of the lamellar phase. We predict that at low
shear rates the parallel orientation appears to be stable. We show that there
is a critical value of the shear rate at which the parallel orientation loses
its stability and the perpendicular one appears immediately below the spinodal.
We associate this transition with a crossover from the fluctuation to the
mean-field behaviour. At lower temperatures the stability of the parallel
orientation is restored. We find that the region of stability of the
perpendicular orientation rapidly decreases as shear rate increases. This
behaviour might be misinterpreted as an additional perpendicular to parallel
transition recently discussed in literature.Comment: 25 pages, 4 figures, submitted to Phys. Rev.
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Characterizing the Catalytic Potential of Deinococcus, Arthrobacter and other Robust Bacteria in Contaminated Subsurface Environments of the Hanford Site
Until recently, there have been no clear physiologic predictors of a cell's ability to recover from ionizing radiation (IR), desiccation, and other DOE-relevant oxidative stress conditions. In general, the most resistant bacteria have been Gram-positive (e.g., Deinococcus, Arthrobacter, Lactobacillus & Enterococcus spp.) and the most sensitive have been Gram-negative (e.g., Pseudomonas, Shewanella & Neisseria spp.). However, there are several reported exceptions to this paradigm, the Gram-negative cyanobacterium Chroococcidiopsis is extremely resistant to IR, whereas the Gram-positive Micrococcus luteus is sensitive. We have identified biomolecular signatures for radiation sensitivity and resistance which are independent of phylogeny, where very high and very low intracellular Mn/Fe concentration ratios correlated with very high and very low resistances, respectively; and restricting Mn(II) in the famously resistant Deinococcus radiodurans sensitized this eubacterium to IR (http://cfyn.ifas.ufl.edu/radiation.pdf)
Grain boundary motion in layered phases
We study the motion of a grain boundary that separates two sets of mutually
perpendicular rolls in Rayleigh-B\'enard convection above onset. The problem is
treated either analytically from the corresponding amplitude equations, or
numerically by solving the Swift-Hohenberg equation. We find that if the rolls
are curved by a slow transversal modulation, a net translation of the boundary
follows. We show analytically that although this motion is a nonlinear effect,
it occurs in a time scale much shorter than that of the linear relaxation of
the curved rolls. The total distance traveled by the boundary scales as
, where is the reduced Rayleigh number. We obtain
analytical expressions for the relaxation rate of the modulation and for the
time dependent traveling velocity of the boundary, and especially their
dependence on wavenumber. The results agree well with direct numerical
solutions of the Swift-Hohenberg equation. We finally discuss the implications
of our results on the coarsening rate of an ensemble of differently oriented
domains in which grain boundary motion through curved rolls is the dominant
coarsening mechanism.Comment: 16 pages, 5 figure
Interfaces of Modulated Phases
Numerically minimizing a continuous free-energy functional which yields
several modulated phases, we obtain the order-parameter profiles and
interfacial free energies of symmetric and non-symmetric tilt boundaries within
the lamellar phase, and of interfaces between coexisting lamellar, hexagonal,
and disordered phases. Our findings agree well with chevron, omega, and
T-junction tilt-boundary morphologies observed in diblock copolymers and
magnetic garnet films.Comment: 4 page
Pore-Scale Characterization of Biogeochemical Controls on Iron and Uranium Speciation under Flow Conditions
Etched silicon microfluidic pore network models (micromodels) with controlled chemical and redox gradients, mineralogy, and microbiology under continuous flow conditions are used for the incremental development of complex microenvironments that simulate subsurface conditions. We demonstrate the colonization of micromodel pore spaces by an anaerobic Fe(III)-reducing bacterial species (Geobacter sulfurreducens) and the enzymatic reduction of a bioavailable Fe(III) phase within this environment. Using both Xray microprobe and X-ray absorption spectroscopy, we investigate the combined effects of the precipitated Fe(III) phases and the microbial population on uranium biogeochemistry under flow conditions. Precipitated Fe(III) phases within the micromodel were most effectively reduced in the presence of an electron shuttle (AQDS), and Fe(II) ions adsorbed onto the precipitated mineral surface without inducing any structural change. In the absence of Fe(III), U(VI) was effectively reduced by the microbial population to insoluble U(IV), which was precipitated in discrete regions associated with biomass. In the presence of Fe(III) phases, however, both U(IV) and U(VI) could be detected associated with biomass, suggesting reoxidation of U(IV) by localized Fe(III) phases. These results demonstrate the importance of the spatial localization of biomass and redox active metals, and illustrate the key effects of pore-scale processes on contaminant fate and reactive transport
Characterization of an electron conduit between bacteria and the extracellular environment
A number of species of Gram-negative bacteria can use insoluble minerals of Fe(III) and Mn(IV) as extracellular respiratory electron acceptors. In some species of Shewanella, deca-heme electron transfer proteins lie at the extracellular face of the outer membrane (OM), where they can interact with insoluble substrates. To reduce extracellular substrates, these redox proteins must be charged by the inner membrane/periplasmic electron transfer system. Here, we present a spectro-potentiometric characterization of a trans-OM icosa-heme complex, MtrCAB, and demonstrate its capacity to move electrons across a lipid bilayer after incorporation into proteoliposomes. We also show that a stable MtrAB subcomplex can assemble in the absence of MtrC; an MtrBC subcomplex is not assembled in the absence of MtrA; and MtrA is only associated to the membrane in cells when MtrB is present. We propose a model for the modular organization of the MtrCAB complex in which MtrC is an extracellular element that mediates electron transfer to extracellular substrates and MtrB is a trans-OM spanning ß-barrel protein that serves as a sheath, within which MtrA and MtrC exchange electrons. We have identified the MtrAB module in a range of bacterial phyla, suggesting that it is widely used in electron exchange with the extracellular environment
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